Doubly Cavitand-Capped Zn-Porphyrin Capsule with Simultaneous Encapsulation of Guest and Ligand, and Its Application to Doubly Cavitand-Capped Double-Decker Zn-Porphyrin Capsule

A 1 : 2 mixture of Zn-meso-tetrakis(4-dodecyl-3,5-dihydroxyphenyl)porphyrin (1-Zn) and tetrakis(4-pyridylethynyl)cavitand (2) in C6D6 self-assembles quantitatively into the doubly cavitand-capped Zn-porphyrin capsule 2 . 1-Zn . 2 with two cavities divided by the porphyrin ring via eight ArOH...Npy hydrogen bonds. Simultaneous encapsulation of 1-acetoxy-3,5-dimethoxybenzene (G) and 4-(4-methylphenyl)pyridine (L2) in 2 . 1-Zn . 2 preferentially occurs to form G/L2@(2 . 1-Zn . 2). A 1 : 1 mixture of 1-Zn and 2 in the presence of G and L2 self-assembles into the G-encapsulating half-capsule G@(2 . 1-Zn) . L2 with coordination of L2 at the outer side of 2 . 1-Zn. A 2 : 2 : 1 mixture of 1-Zn, 2, and 1,4-diazabicyclo[2.2.2]octane (L3) in the presence of G self-assembles preferentially into the G-encapsulating doubly cavitand-capped double-decker Zn-porphyrin capsule G/G@(2 . 1-Zn . L3 . 1-Zn . 2) with coordination of L3 between two hydrogen-bonded 1-Zn subunits. Thus, selective formation of these cavitand-porphyrin capsules can be controlled by the stoichiometry of 1-Zn and 2 as well as the character of N-ligands.

Automated summary

Selective formation of these cavitand-porphyrin capsules can be controlled by the stoichiometry of 1-Zn and 2 as well as the character of N-ligands.